The present invention generally relates to the synthesis of commodity and specialty polymeric materials. Specifically, the present invention relates to manufacture of polymers with hyperbranched architecture from telomerization.
Highly branched polymers and copolymers have attracted considerable attention over the past decades, since many advanced materials with new or improved properties can be obtained therefrom. The terms xe2x80x9chyperbranchedxe2x80x9d and xe2x80x9chighly branchedxe2x80x9d used herein with respect to branched polymers are intended to designate polymers having a relatively high percentage of propagated branching sites per number of polymerized monomer units, e.g. at least one branching site per every ten monomer units, preferably at least one branching site per every five monomer units and more preferably at least one branching site per every three monomer units. Highly branched polymers can be made by multi-step or one step processes. Multi-step generation processes were exemplified by Frechet in U.S. Pat. No. 5,041,516 and by Hult in U.S. Pat. No. 5,418,301. Both patents described that the highly branched polymers known as dendrimer or xe2x80x9cstarburst polymerxe2x80x9d were made through a series of growth steps consisting of repeatedly reacting, isolating, and purifying.
One-step process was first conceptualized by Flory (J. Am. Chem. Soc., 74, p2718 (1952)) who demonstrated by theoretical analysis that highly branched and soluble polymers could be formed from monomers comprising the structure AB2, where A and B are reactive groups, by one-step condensation polymerization. In contrast to dendrimers, the polymer formed by AB2 polymerization is randomly branched.
Frechet et al disclosed that vinyl hyperbranched polymers could be obtained by means of living chain polymerization of AB monomers (Frechet et al. U.S. Pat. Nos. 5,587,441, 5,587,446), which was termed as self-condensation vinyl polymerization. AB monomer was defined as one that contains two reactive groups, A and B, in the same molecule, which react independently of each other within a molecule. The A group is typically a polymerizable vinyl group and the B group is a reactive group that can be activated by an activator and add to the A group to promote the polymerization. The general mechanism of formation of hyperbranched polymer can be described in accordance with Scheme 1 below, where the A group is a polymerizable vinyl group. 
As indicated in Scheme 1 above, B with AB vinyl monomer, a B group may be activated to a B* moiety that itself is capable of initiating the polymerization of a vinyl monomer. The polymerization process is initiated by reaction of one initiating B* group with the double bond A of another AB* monomer unit to yield the dimer. The dimer now has one vinyl group and two reactive sites, and subsequently functions like an AB2-monomer. Additional condensation of dimer, trimer, and eventually larger oligomeric species produced by sequential condensations gives rise to a hyperbranched polymer. The polymerization of AB monomer described by Frechet displays a xe2x80x9cliving-likexe2x80x9d character, as side reactions such as chain transfer and elimination are substantially eliminated. Based on the same mechanism as Frechet""s, a number of vinyl hyperbranched polymers have been prepared by various living polymerization processes, such as atom transfer radical polymerization (Wang, et al. U.S. Pat. No. 5,807,937 (1998)), group transfer polymerization (Muller, et al. Polymer Preprint, 38(1), 498 (1997)), and stable radical polymerization (Hawker et al. J. Am. Chem. Soc. 113, 4583 (1991)).
There are, however, disadvantages associated with the polymerization processes described in the prior art for the manufacture of vinylic hyperbranched polymers by living polymerization processes. First, in the cases of living anionic, cationic, and group-transfer polymerization, the polymerizations systems need to be very pure. In the case of living cationic and group transfer polymerization, e.g., a trace of impurity such as water often prevents polymerization from proceeding, so often that there is even no polymer obtained. Thus, these living polymerization processes are not preferred in industrial productions. Second, the use of heavy metal containing inorganic salts in atom transfer radical polymerization is not environmentally friendly and practical.
In 1946, Handford first defined telomerization as the reaction between a compound XY called the telogen and one or several molecules of polymerizable species M called the taxogen, under polymerization conditions which lead to the formation of telomers Xxe2x80x94(M)nxe2x80x94Y (U.S. Pat. No. 2,396,786). Telomerization is generally regarded as chain reaction that, in contrast to polymerization, leads to oligomers having very low molecular weight, and even monoaddition compounds, which are referred to as telomers. The general mechanism of formation of telomer can be described in accordance with Scheme 2 below. 
In Scheme 2, Initiator I (e.g., a peroxide, a peracid, or a diazoic compound) generates activated species R* (e.g., free radical group). R* then reacts with telogen XY to form activated species X* and Rxe2x80x94Y. X* can then react with taxogen M monomer to form species Xxe2x80x94M*, which can react with further M monomers through propagation to form oligomeric species Xxe2x80x94M(nxe2x88x921)xe2x80x94M*. Xxe2x80x94M(nxe2x88x921)xe2x80x94M* species upon transfer reaction with telogen XY forms telomer Xxe2x80x94Mnxe2x80x94Y and activated species X*, which can then initiate further telomerization. The reaction can terminate by combination of two Xxe2x80x94M(nxe2x88x921)xe2x80x94M* and/or Xxe2x80x94M* species to form non-activated species. The average degree of chain growth (n) in telomerization is generally from 2 to about 100, more typically 2 to 30, or even 2 to 10, dependent upon the relative reaction rates for the propagation and chain transfer steps. Telomerization generally requires that the chain growth (propagation) and chain transfer steps have reaction rates within two orders of magnitude of each other, as if the propagation reaction rate is too fast relative to the chain transfer reaction rate, regular polymerization will occur. If the chain transfer reaction rate is significantly faster than the propagation reaction rate, on the other hand, a 1:1 adduct (i.e., Xxe2x80x94Mxe2x80x94Y) will be obtained.
The telomerization products can thus be classified as intermediate between organic monomeric and macromolecular polymeric compounds and have been found in wide industrial applications (Stark, Free Radical Telomerization, Academic Press, Inc., New York, 1974; Boutevin et al, in Comprehensive Polymer Science, Pergamon: Oxford, 1991, vol. 3, p 185). However, no prior art discloses the synthesis of hyperbranched polymer by telomerization.
It would be desirable to provide a simple, practical, and environmentally friendly process for the manufacture of soluble hyperbranched polymers. Accordingly, one object of the present invention is to make hyperbranched polymers by telomerization.
The invention comprises a process for making hyperbranched polymers from Anxe2x80x94Lz(XY)m type monomers wherein A is a polymerizable group moiety, XY is a telogen group moiety in which Y is a transferable atom or group which can participate in a transfer reaction with the formation of reactive X*, L is a linkage between A and XY, z is 0 or 1, and n and m are integers of at least 1, comprising
(a) initiating reaction by forming activated species from reaction between either an A or an XY group of the Anxe2x80x94Lz(XY)m type monomer and an external stimulus to form activated monomer species with an activated polymerizable group moiety A* or an activated moiety X* derived from the telogen group moiety XY; and
(b) polymer segment chain growth by
(i) propagation reaction between the polymerizable group A moieties of the Anxe2x80x94Lz(XY)m type monomers with the activated moieties A* and X* of activated species, and further reaction between the polymerizable group moieties with the activated moieties of the reaction products thereof, and
(ii) chain transfer reaction between the activated A* polymerizable group moieties of activated species or of polymer segments formed in (b)(i) with XY telogen group moieties of the Anxe2x80x94Lz(XY)m type monomers or of polymer segments formed in (b)(i), whereby activated X* moieties and inactive Axe2x80x94Y moieties are formed by transfer of transferable atom or group Y of the telogen group moiety XY to the activated A* moiety;
wherein the reaction rates of the (b)(i) propagation reaction and of the (b)(ii) chain transfer reaction are within 2 orders of magnitude of each other, more preferably within one order of magnitude of each other, such that the combination of propagation reaction and chain transfer reaction results in formation of a highly branched polymer from the Anxe2x80x94Lz(XY)m type monomer.
The present invention provides a process which is adaptable to manufacture of hyperbranched materials with existing scale-up and commercialization facilities, and which may rely upon readily available starting materials and catalysts. The present invention provides a process by which a broad variety of functional hyperbranched polymers may be obtained, a process for making hyperbranched polymers in which a broad variety of macro-initiators may be employed, and enables the manufacture of hyperbranched polymers useful in a wide variety of known and novel applications.
The present invention discloses a new process to make hyperbranched polymers and related products by means of telomerization reaction of Anxe2x80x94Lz(XY)m type of monomers where A is a polymerizable group and XY is a telogen-like moiety in which Y is a transferable atom or group which can participate in a transfer reaction with the formation of reactive X*, L is a linkage between A and XY, z is 0 or 1, and n and m are integers of at least 1, preferably 1 to 2, and most preferably n is 1 and m is 1 or 2. For ease of reference purposes the terms xe2x80x9cAxe2x80x94XY type monomerxe2x80x9d or xe2x80x9cAxe2x80x94XY monomerxe2x80x9d may be used in the description of the invention in reference to such monomers, without intent to limit such reference to monomers having only a single A group and single XY group. Where the present invention is described in the context of use of Axe2x80x94XY type monomers which comprise a single polymerizable group A and a single telogen group XY for simplicity purposes, it will be understood by the artisan that the Axe2x80x94XY type monomer employed in accordance with the present invention may be selected from compounds which may have multiple A and/or XY groups in accordance with the general formula above.
While not intending to be limited to any particular initiating/catalyst systems or monomers, the synthesis of hyperbranched polymer via telomerization of Axe2x80x94XY monomer can be understood by the following discussion.
Similar to other types of chain polymerization processes, the telomerization of Axe2x80x94XY monomers will typically include the steps of initiation, chain growth, chain transfer, and termination.
Initiation
In this step, the initiating species A*xe2x80x94XY or Axe2x80x94X* is formed from reaction between either A moiety or XY group and an external stimulus:
Axe2x80x94XYxe2x86x92*Axe2x80x94XY
Axe2x80x94XYxe2x86x92Axe2x80x94X*+Yxe2x80x2
where Yxe2x80x2 is an inactive species derived from transferable group Y.
Propagation
The first step of the chain growth begins with addition of the initiating species A*xe2x80x94XY or Axe2x80x94X* with monomer Axe2x80x94XY or Axe2x80x94X*: 
Hyperbranched polymer is subsequently formed by reacting above -described active species with the A groups in either additional monomer or of growing polymer segments: 
Chain Transfer
Similarly as in telomerization as described in the prior art, the process of the invention includes a chain transfer reaction between activated polymerizable group moieties of polymer segments with telogen group XY moieties whereby activated X* moieties and deactivated polymerizable group moieties are formed by transfer of transferable atom or group Y of the telogen group moiety XY to the activated polymerizable group moiety, wherein the reaction rates of the propagation and chain transfer reactions are within 2 orders of magnitude of each other, more preferably within one order of magnitude of each other. Both growth and transfer may be either very fast or very slow; the absolute rate is not limiting as it is only the ratio of growth to transfer which is accountable for the formation of hyperbranched polymer.
Termination
In the present process, termination reactions may also often occur along with the propagation and chain transfer reactions during the course of telomerization. Similarly as in prior art telomerization processes, termination reaction may result from combination of two activated moiety species to form non-activated species. While termination reactions may occur to some extent, chain transfer reaction in the process of the invention desirably should be faster than termination reaction to the point that excessive crosslinking reactions are avoided so that soluble polymers may be obtained.
The polymers which result from the present process are clearly different from those that result from conventional telomerization of M monomers in the presence of separate telogen XY. In present process, the telogen-like XY group is part of the monomer and consequently the resultant hyperbranched polymer is composed of X in the backbone as part of repeating monomeric units and multi-functional Y at the ends, whereas the conventional telomerization only yields telomer containing X and Y at each end of the telomer. Also, the hyperbranched polymer may possess multi-functional XY moiety, whereas there is no XY moiety in conventional telomer.
The present process is also clearly distinguished from xe2x80x9clivingxe2x80x9d polymerization of AB type monomers, where both A and B of AB monomer are required to be able to be reversibly activated and deactivated and wherein reactants and catalysts are uniquely selected so as to maximize the rate of propagation reaction relative to chain transfer and termination reactions. In comparison to living polymerization of AB monomers, the present invention can advantageously yield hyperbranched polymers under conventional telomerization conditions employing less restrictive reactant and catalysts selection criteria. While the telomerization chain transfer reaction between xe2x80x94A* and xe2x80x94XY moieties yields an xe2x80x94Axe2x80x94Y moiety which is a xe2x80x9cdeadxe2x80x9d species that is not further reactivated (unlike the reactions in living polymerization process of AB monomer), as the XY telogen group moieties in accordance with the invention process are part of the reactant monomer or a subsequently grown polymer segment, the chain transfer reaction does not necessarily end growth of polymer chain segments as in the prior art telomerization process, but rather transfers subsequent growth to branching at the X* site which is created by the chain transfer reaction. A sufficiently fast chain transfer reaction between active species xe2x80x94A* and xe2x80x94XY moieties (relative to propagation and termination reactions) in the present invention leads to the generation of multi-functional active centers and subsequently of hyperbranched polymer without forming insoluble cross-linked polymers. In comparison to living polymerization of AB monomers, the present invention can advantageously yield hyperbranched polymers under conventional telomerization or xe2x80x9cnon-livingxe2x80x9d polymerization conditions.
In addition to the actual structure of the Axe2x80x94XY type monomer, the relative reaction rates between the propagation, chain transfer and termination reactions which may occur in the process of the invention can be affected by (but not limited to) the following polymerization conditions: the reactivity and concentration of comonomer(s); the reactivity of catalyst; the concentration of catalyst; the concentration of monomer; polymerization temperature; polymerization pressure; polymerization time; polymerization equipment; polymerization technology; monomer addition method and sequence; the solvent; the additives; the mixing methods. Combinatorial chemistry and experimental design can be used to explore and optimize suitable catalyst system and experimental conditions for telomerization in accordance with the present invention, in combination with selection of suitable monomer structure for obtaining hyperbranched polymer materials with desired properties.
While for simplicity the present invention is primarily described in the context of use of Axe2x80x94XY type monomers which comprise a single polymerizable group A and a single telogen group XY, the Axe2x80x94XY type monomer employed in accordance with the present invention may be selected from any compound having the following formula:
Anxe2x80x94Lz(XY)m
wherein A is a polymerizable group, XY is a telogen group in which Y is a transferable atom or group which can participate in any transfer reaction with the formation of reactive X*, L is a linkage between A and XY, z is 0 or 1, and n and m are integers of at least 1, preferably 1 to 2, and most preferably n is 1 and m is 1 or 2.
In a preferred embodiment, the A group is any one that may undergo chain polymerization/telomerization such as those described in Principle of Polymerization (Ordian). They may include, but are not limited to, vinylic, cyclic ether, siloxane, and cyclic imino ether groups. In a preferred embodiment, the A group is selected from one of the following formula: 
wherein R1, R2 and R3 are independently selected from the group consisting of H, halogen, CN, straight or branched C1-C20 alkyl and C6-C20 aryl that may be substituted with halogen. In a particularly preferred embodiment, the A group has the formula: 
wherein R1, R2 and R 3 are as defined above. In a most preferred embodiment, the A group has the formula: CH2xe2x95x90CHxe2x80x94.
The xe2x80x94XY group is a telogen-like group with Y being a transferable atom or group such as described in Free Radical Telomerization (Stark) and other prior art telomerization processes. The xe2x80x94XY moiety is required to be capable of forming xe2x80x94X* by any means such as heat, light, electron beam/radiation, microwave, or by reacting xe2x80x94XY with an external active moiety such as an anion, a cation, a radical, or other activation source. In order to form hyperbranched polymer in the present process, the resultant xe2x80x94X* must be capable of reacting with above-described A polymerizable group of to form a new active species xe2x80x94Xxe2x80x94A*.
The transferable atom or group Y may be, e.g., H, halogen (i.e., F, Cl, Br, I), Li+, Na+, K+, Cs+, OCxe2x95x90NC6H4S, (Ph)2R4C (where R4=CN, OPh, OSiMe3), R5 (where R5=alkyl, aryl), (R5)2NC(xe2x95x90S)xe2x80x94S, VR5 (where V=Se, Te), R5S, OR5, Si(R5)3, or Oxe2x80x94N(R6)2 (where the two R6 groups may be independently alkyl or aryl, or may be joined to form a heterocyclic ring). In a more preferred embodiment, Y is H, Cl or Br, and most preferably Cl or Br.
The telogen group xe2x80x94XY may be, e.g., xe2x80x94OM (where M is H, Li+, Na+, K+, Cs+), xe2x80x94CZ3( where Z=Cl, Br, I), xe2x80x94CF2Z, xe2x80x94CCl2Br, xe2x80x94CBr2Cl, xe2x80x94OC(O)CZ2, xe2x80x94C(O)xe2x80x94Z2, xe2x80x94CH2-qZq(where q is an integer of 0-2), xe2x80x94C(O)CH2-qZq, xe2x80x94C(O)OCH2-qZq, xe2x80x94OC(O)CH2-qZq, xe2x80x94SO2Cl, (R5)2NC(xe2x95x90S)xe2x80x94Sxe2x80x94Sxe2x80x94C(xe2x95x90S)N(R5)2xe2x80x94, R5Sxe2x80x94SR5xe2x80x94, (R5)2NC(xe2x95x90S)xe2x80x94Sxe2x80x94R5xe2x80x94, R5Sxe2x80x94R5xe2x80x94, xe2x80x94R5xe2x80x94Oxe2x80x94N(R6)2. In most preferred embodiments, XY is selected from the group consisting of xe2x80x94OH, xe2x80x94CCl3, xe2x80x94CBr3, xe2x80x94CCl2Br, xe2x80x94CBr2Cl, xe2x80x94OC(O)CBr2, xe2x80x94OC(O)CCl2.
L is a linking group, which may be selected, e.g., from any of further substituted or unsubstituted straight or branched alkyl, alkylene, and aryl group. Representative possible substituents include halogen and CN. In a preferred embodiment, L is selected from: xe2x80x94(CH2)1-21xe2x80x94, xe2x80x94OC(O)(CH2)0-10xe2x80x94, xe2x80x94C(O)(CH2)0-10xe2x80x94, xe2x80x94Oxe2x80x94, xe2x80x94C(O)Oxe2x80x94(CH2)0-10xe2x80x94, xe2x80x94C(O)O(CH2)2N(CH3)xe2x80x94, xe2x80x94C(O)N(R7)xe2x80x94(where R7=H, alkyl), xe2x80x94C6F4xe2x80x94; 
In another embodiment, L may be selected from any of oligomer or polymer chains derived from any kinds of polymerizable monomers. In a more preferred embodiment, L may be a polystyrene, polyolefin, polyisobutylene, salt or ester of poly(meth)acrylic acid chain with molecular weight from 200 to 20,000.
In another more preferred embodiment, L may be selected from any of oligomer or polymer chains having the following repeating units: 
wherein b and c are integers of 0 to 18, Ar1 and Ar2 are independent aryl selected from phenyl, naphthyl, biphenyl, which may be substituted with C1-C6 alkyl, C1-C6 alkoxy, halo, or acetoxy.
In still another more preferred embodiment, L is selected from any of oligomer or polymer chains having the following repeating units: 
wherein d is equal 0 or 1, R8 is selected from any group consisting of O, S, SO2, CH2, or CO; and R9 is H, aryl and straight or branched C1-C20 alkyl which may be substituted with halogen, and R10 is aryl and straight or branched C1-C20 alkyl.
The present invention may be carried out with any conventional chain polymerization catalyst or the activated moieties in present process may be generated by using known sources such as heat, light, electron beam/radiation, microwave, such that the polymerization may be carried out by any conventional mechanism such as cationic, anionic, radical, and ring-opening. In a preferred embodiment of the invention, the activated species formed in step (a) comprise free radical groups and the polymerization proceeds by free radical polymerization. Any catalyst or initiating system that is well known in the art of chain polymerization such as those described in Principles of Polymerization, 3rd Ed, by Ordian (Wiley) and which does not induce living polymerization process is suitable for use in the present invention. Examples of these catalysts or initiating systems are but not limited those as described following.
Radical initiators can be generated by such methods as thermally induced homolytic scission of a suitable compound or compounds (thermal initiators such as peroxides, peroxyesters, or azo compounds), the spontaneous generation from polymerizable group (e.g., styrenics), redox initiating systems, photochemical initiating systems or high energy radiation such as electron beam, X- or gamma-radiation. Examples of thermal initiators are one or more of the following compounds: 2,2xe2x80x2-azobis(isobutyronitrile), 2,2xe2x80x2-azobis(2-cyano-2-butane), dimethyl 2,2xe2x80x2-azobisdimethylisobutyrate, 4,4xe2x80x2-azobis(4-cyanopentanoic acid), 1,1xe2x80x2-azobis(cyclohexanecarbonitrile), 2-(t-butylazo)-2-cyanopropane, 2,2xe2x80x2-azobis(2-methyl-N-1,1-bis(hydroxymethyl)2-hydroxyethyl)propionamide, 2,2xe2x80x2-azobis(N,Nxe2x80x2-dimethyleneisobutyramine)dihydrochloride, 2,2xe2x80x2-azobis(2-amidinopropane)dihydrochloride, 2,2 xe2x80x2-azobis(N,Nxe2x80x2-dimethyleneisobutyramine), 2,2 xe2x80x2-azobis(2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide), 2,2xe2x80x2-azobis(2-methylpropane), t-butyl peroxyacetate, t-butyl peroxybenzonate, t-butyl peroxyoctoate, t-butyl peroxyneodecanoate, t-butyl peroxyisobutyrate, t-butyl peroxypivalate, t-amyl peroxypivalate, di-isopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, dicumyl peroxide, dibenzoyl peroxide, dilauroyl peroxide, potassium peroxyldisulfate, ammonium peroxydisulfate, di-t-butyl hyponitrite, dicumyl hyponitrite. Examples of photochemical initiator systems are one or more of the following benzoin derivatives, benzophonenone, acyl phosphite oxides, and photoredox system. Examples of redox initiator systems can include combinations of the following oxidants and reductants. Oxidants: sodium peroxydisulfate, potassium peroxydisulfate, hydrogen peroxide, t-butyl hydroperoxide. Reductants: iron (II), titanium (III), potassium thiosulfite, sodium, potassium bisulfite. Other redox initiating system may be those organic-inorganic redox pairs which may include: 1), oxidation of thiol compound combined with Fe3+, Ce4+, BrO3xe2x88x92 and S2O82xe2x88x92 containing inorganic compounds; 2), oxidation of aldehydes and ketones by Ce4+ and V5+, 3), oxidation of oxalic, malonic, and citric acids by permanganate and Mn3+; 4) transitional metal chelates, organometallic derivatives of transition metals in low oxidation states.
Cationic telomerization initiators are selected from those which can bring about the telomerization of monomers with electron-releasing substitutents. Examples of cationic telomerization initiators are those as described in the following. Protonic acids may be selected from those very string protonic acids such as concentrated sulfuric acid, trifluoroacetic acid, fluorosulfuric acid, and trifluoromethane sulfonic acid. A variety of Lewis acids can be used in the present invention. Examples of these Lewis acid are metal halides such as AlCl3, BF3, SnCl4, SbCl5, ZnCl2, TiCl4, PCl5; organometallic derivatives such as R19AlCl2, R192AlCl, R193Al, R19ZnOZnR19, R192AlOAlR192 (where R19 is alkyl, haloaklyl); and oxyhalides such as POCl3, CrO2Cl, SOCl2, VOCl3; oxonium ions such as Et3O(BF4). Initiation by Lewis acids either requires or proceeds faster in the presence of either a donor such as water, alcohol, and organic acid, or a cation donor such as t-butyl chloride or triphenylmethyl fluoride. Other cationic systems may include acetyl perchlorate, iodine, electrolytic initiation, and ionizing radiation.
A variety of basic initiators can be used in the present invention to initiate anionic telomerization of Txe2x80x94M monomers. These include but not limited to covalent and ionic metal amides such as Li(Na, K)NH2, Li(Na, K)NEt2, alkoxides and phenoxides such as R20OLi (Na, K) (where R20 is alkyl, aryl), hydroxides such as Li (Na, K)OH, cyanides, phophines, and amines, organometallic compounds such as R19Li, R20MgXxe2x80x2 (Xxe2x80x2 is halogens).
The Zigler-Natta catalysts can also be used in the present invention. These encompass literally thousands of different combinations of a Group I-III organometallic compound (or hydride) and a compound of a Group IV-VIII transition metal such as those described in Principles of Polymerization, 3rd Ed, by Ordian (Wiley).
Metallocene-based catalytic systems can be used in the present invention. Examples are those systems composed of a metallocene and an alumoxane.
Late metal catalysts developed by Brookhart and others can also be used in the present invention. These catalysts are usually composed of complexes of Ni or Pd or other late metal with chelating agents such as diimines (Johnson, J. Am. Chem. Soc. 117, 6416 (1995)).
The present telomerization process may be conducted in the absence of solvent known as bulk polymerization. However, it can be also carried in any solvent, which might include but not limited to ethers, cyclic ethers, alkanes, cycloalkanes which may be substituted, aromatic solvents, halogenated hydrocarbon solvents, acetonitrile, dimethylformamide, ethylene carbonate, dimethylsulfoxide, dimethylsulfone, alcohol, water, mixture of such solvents, and supercritical solvents such as carbon dioxide, alkanes in which any H may be replaced with F, etc. The present telomerization may also be conducted in accordance with known suspension, emulsion, microemulsion, gas phase, dispersion, precipitation, template, reactive injection molding, phase transfer polymerization processes and the like. Polymerization can be terminated by any known conventional methods.
The polymerization can be conducted in accordance with known batch, semi-batch, continuing processes and the like. The polymerization temperature can generally be varied from xe2x88x92100 to 200xc2x0 C. and polymerization pressure from 10xe2x88x928atm to 103atm. Combinatorial chemistry and experimental design can be used in the context of the present invention to optimize the polymerization reaction conditions.
The molecular weight and molecular distribution of polymers prepared with present invention typically will be from 100 to 106 and from 1.001 to 100, respectively. The final polymers can be purified with known processes such as precipitation, extraction, and the like. Polymers can be used in the forms of solid particle, solution, dispersion, latex, and the like.
In a preferred embodiment, the present invention provides a process to make copolymers from co-telomerization of two or more than two Axe2x80x94XY type monomers or from co-telomerization of Axe2x80x94XY type monomer with xe2x80x9cordinaryxe2x80x9d monomer including macromonomer.
The preferred xe2x80x9cordinaryxe2x80x9d monomers include carboxyl group-containing unsaturated monomers such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, and the like(preferably methacrylic acid), C2-8 hydroxyl alkyl esters of (meth)acrylic acid (preferably methacrylic acid) such as 2-hydroxylethyl (meth)acrylate, 2-hydroxylpropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate and the like, monoesters between a polyether polyol (e.g., polyethylene glycol, polypropylene glycol or polybutylene glycol) and an unsaturated carboxylic acid (preferably methacrylic acid); monoethers between a polyether polyol (e.g., polyethylene glycol, polypropylene glycol or polybutylene glycol) and a hydroxyl group-containing unsaturated monomers (e.g., 2-hydroxyl methacrylate); adducts between an unsaturated carboxylic acid and a monoepoxy compound; adducts between glycidyl (meth)acrylates (preferably methacrylate) and a monobasic acid (e.g., acetic acid, propionic acid, p-t-butylbenzonic acid or a fatty acid); monoesters or diesters between an acid anhydride group-containing unsaturated compounds (e.g., maleic anhydride or iraconic anhydride) and a glycol (e.g. ethylene glycol, 1,6-hexaediol or neopentyl glycol); chlorine-, bromine-, fluorine-, and hydroxyl group containing monomers such as 3-chloro-2-hydroxylpropyl (meth)acrylate (preferably methacrylate) and the like; C1-24 alkyl esters or cycloalkyl esters of (meth)acrylic acid (preferably methacrylic acid), such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-, sec-, or t-butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, octylmethacrylate, decyl methacrylate, lauryl methacrylate, stearyl methacrylate, cyclohexyl methacrylate and the like, C2-18 alkoxyalkyl esters of (meth)acrylic acid (preferably methacrylic acid), such as methoxybutyl methacrylate, methoxyethyl methacrylate, ethoxyethyl methacrylate, ethoxybutyl methacrylate and the like; olefines or dines compounds such as ethylene, propylene, butylene, isobutene, isoprene, chlororene, fluorine containing olefins, vinyl chloride, and the like; ring-containing unsaturated monomers such as styrene and o-,m-,p-substitution products thereof such as N,N-dimethylaminostyrene, aminostyrene, hydroxystyrene, t-butylstyrene, carboxystyrene and the like, a-methyl styrene, phenyl (meth)acrylates, nitro-containing alkyl (meth)acrylates such as N,N-dimethyl-aminoethyl methacrylate, N-t-butylaminoethyl methacrylate; 2-(dimethylamino)ethyl methacrylate, methyl chloride quaternized salt, and the like; polymerizable amides such as (meth)acrylamide, N-methyl(meth)acrylamide, 2-acryloamido-2-methyl-1-propanesulfonic acid, and the like; nitrogen-containing monomers such as 2-, 4-vinyl pyridines, 1-vinyl-2-pyrrolidone, (meth)acrylonitrile, and the like; glycidyl group-containing vinyl monomers such as glycidyl (meth)acrylates and the like, vinyl ethers, vinyl acetate, epoxides, cyclosiloxanes, cyclic ethers, cyclic imino ethers.
The preferred xe2x80x9cordinaryxe2x80x9d macromonomer include those defined in xe2x80x9cChemistry and Industry of Macromonomersxe2x80x9d (Yamashita, Huthig and Wepf, New York ,1993).
The process of the present invention also may be used for the formation of a variety of prepolymers or precursors such as macromonomer and macro-initiator, which can further react with other monomers via a variety of step or chain polymerization processes with the formation of graft (comb) polymers, block copolymers, star polymers, crosslinking polymers, IPNs, semi-IPNs, and the like. In another preferred embodiment, the polymers prepared in the present invention may be used as multi-functional polymeric telogens in telomerization to make polymers with a variety of topological architectures such as block copolymer, graft copolymer, star polymer, branched and hyperbranched polymer, etc.
In another embodiment, the polymers prepared in the present invention can be used as polymeric coupling agents to make polymers with a variety of topological architectures such as block copolymer, graft copolymer, star polymer with hyperbranched nature.
In a further embodiment, the polymers prepared in accordance with the present invention can be used as a macroinitiator in various living or controlled polymerization such as atom transfer radical polymerization (Wang, J.
Am. Chem. Soc.,), RAFT polymerization (Chiefari, Macromolecules, 31, 5559 (1998)), Inifieter radical and cationic polymerization (Otsu, T.; Eur. Polym. J., 31, 67 (1995)), and other non-living or non-controlled chain or condensation polymerization processes to make polymers with a variety of topological architectures such as block copolymer, graft copolymer, star polymer, branched and hyperbranched polymer, crosslinking polymers, gel, shell-core, etc.
In another embodiment, functional polymers such as multi-end functional polymers and in-chain functional polymers can be prepared with the present invention. Also, highly branched polymers with photographically useful end groups as described in U.S. Pat. No. 6,252,025 can be also made via present invention.
The polymers and copolymers prepared in the present invention can be used in a variety of applications such as plastics, elastomers, fibers, engineering resins, coatings, paints, adhesives, asphalt modifiers, detergents, diagnostic agents and supports, dispersants, emulsifiers, rheology modifiers, viscosity modifiers, in ink and imaging compositions, as leather and cements, lubricants, surfactant, as paper additives, as intermediates for chain extensions such as polyurethanes, as additives in inkjet, printing, optical storage, photography, photoresist, and coloration of polymer, as water treatment chemicals, cosmetics, hair products, personal care products, polymeric dyes, polymeric couplers, polymeric developers, antistatic agents, in food and beverage packaging, pharmaceuticals, carriers for drug and biological materials, slow release agent formulations, crosslinking agents, foams, deodorants, porosity control agents, complexing and chelating agents, carriers for chiral resolution agents, catalysts, carriers for gene transfection, for encapsulation, as light harvesting materials, as non-linear optical materials, to form super macromolecular assemble.